Water-soluble mordant azophthalocyanine dyestuffs and process for making them



United States Patent I r 2,776,957 WATER-SOLUBLE MORDAN T AZOPHTHALOCYA-NINE DYESTUFFS AND PROCESS FOR MAKING THEM Willy Brentano, Arlesheim,and Hans Grossmann and Max Miiller, Basel, Switzerland, assignors toDurand & Huguenin A. G., Basel, Switzerland, :1 Swiss firm No Drawing.Application July 27, 1953, Serial No. 370,612 Claims priority,application Switzerland July 31, 1952 12 Claims. (Cl. 260-446) Thisinvention provides new, Water-soluble, mordant .aao-phthalocyaninedyestuffs which are derived from a phthal-ocyanine tetra-sulphonic:acid, and contain at least one SO2.'NH-- group, at least one azolinkage and at least one salicylic acid group. These dyestufis aresuitable for dyeing or printing textiles and yield green to olive tints.

The dyestuffs of this invention correspond to the general formula sO2.NH o H C O O H in which A represents a substituted or unsubstitutedmetalliferous phthalocyanine molecule in which the -SO2.NH

or the -SO3H groups are present in the 3- or 4-position,

n represents a whole number from 1 to 4, m represents a whole numberfrom 0 to 3, the sum of m-l-n being,

equal to 4, x represents a hydrogen atom, a halogen atom of a methyl,hydroxyl, nitro or sulphonic acid group, y represents a hydrogen atom, ahalogen atom or an :alkyl, alkoxy, nitro, sulphonic acid or carboxylicacid group, and 1 represents .a hydrogen atom, :a halogen atom or analkyl or alkoxy group, and the --'SO2.NH :group occupies a metaorpara-position relatively to the iazo linkage.

The invention also includes a process for making the above dyestuffs,wherein one molecular proportion of a ohthalocyanine sulphochloride ofthe formula in which -A, n and m have the meanings given above, m+nbeingequa'l to 4, is reacted in an aqueous medium and in the presence ofa substance capable of binding mineral acid with at least one, butadvantageously 2 to 4, molecular proportions of at least oneamino-lazodyestufi of the general formula no NH:

in which x, y and z have the meanings given above, and the NH2 groupoccupies a metaor para-position relatively to the az-o linkage.

Among the sulphochlorides of phthalocyanine tetrasulphonic acids used inthe present process there are to he understood those which can be madeby methods in themselves known. As phthalocyanine sulphochloridessuitable for the reaction there. come into consideration especiallycopper-, nickel.- and cob-alt-phthalocyvanines, and also iron, chromiumand alum-inium-phthalocyanines.

2,776,957 Patented Jan. 8, 7

Depending on the method of preparation the sulphochloride groups :arepresent in the 4 or 3-position of the phthalocyanine molecule, and thisdepends on whether a 4-:sulphophtlra-lic acid is used as startingmaterial for preparing them, or whether the sulphochloride gnoups areintroduced by sulphonation or by direct sulphochlorination of thephthalocyanine. The number of sulphochloride groups in the molecule mayrange from 1 to 4. in the preparation of the sulphochlorid-es ofphthalocyanine tetrasulphonic acids, and especially during theirisolation, there are generally obtained mixtures of phthalocyanineshaving a different number of sulphochlonide groups.

Examples of suitable amiuo-lazo dyestufis, which are capable of takingpart in the reaction, are those of the general tormu-la no Nm,

in which at, y and 2 have the meanings given above and the -'NH2 groupoccupies a metaor para-position relatively to the :azo linkage:

3-amino-4 oxy- 1: 1f-azobenzene-s carboxylic acid,

3 amino .2 methyl 4' oxy 1:1 .azobenzene 5'- cai boxylic acid,

.3 amino 3 methyl 4' oxy 1:1 azobenzene 5'- oarboxylic acid,

3-am-ino-4'-oxy1 1Qazobenzene-S' canboxylic acid-G-sulphonic acid, I

3 amino 4 methyl 4 oxy -l:1' azohenzene 5'- carboxylic acid,

3 amino 6 methyl 4' oxy 1:1 azo'benzene 5'- car'boxylic acid,

3 amino 6 methoxy 4' oxy 1:1 -1azo' benzene 5- oanboxylic acid,

3 :amino 6 chloro 4' oxy 1:1 azobenzene 5'- :carboxylic acid,

'4-amino-4'-.oxyl l' azobenzene 5-carboxylic acid,

4 amino 2' methyl 4 oxy 1: 1' lazobenzene 5"- camboxylic acid,

4 amino 3 methyl 4' oxy 1:1 azobenzene 5'- carboxylic acid,

4aamino-4'eoxy l 21Qazobenzene-S'oarhoxylic I acid-Soulphonic acid,

4 amino 2 methyl 4' oxy 1:1" iazob-enzene 5- carboxylic acid,

4 :amino 3 methyl 4' oxy '1':1' -1az'ohenzene 5- carboxylic acid,

4 amino 2 methyl 3' methyl 4' oxy 1:1 azo ibenzene-Y-carboXylic acid,

4 amino 2 methoxy 4' oxy' 1:1 :azdbenzene 5- car boxyl ic acid,

4 amino 3 ethoxy 4' oxy 1:1" azobenzene 5"- carboxylic acid,-

4 amino 2 methyl 5- methoxy 4' oxy 1:1" azubenzene-SoarboXylic acid,

4 lamina 2:5 dimethoxy 4' oxy 11:1 azoben'zene- '5carboxylic acid,

4 amino 2 chlono 4' .oxy 1:1 :azoben'zene 5' canboxylic acid,

4 amino 2'- nitro 4' oxy 1:1 azobenzene 5"- carboxylic acid,

4-amin-o-4--oxy- 1-:lQazobenzeneQzS icarboxylic acid,

4-amino-2' :4'-dioxy-.1 1'-1azorbenzene-5 canboxylic acid,

4 amino 2 methyl 3' chloro 4 oxy -'1:1' azobenzene-Scarboxylic acid,

4 -amino 2 methyl 3' nitro 4' oxy 1:1 azobenzene--carboxylic acid,

4 amino 2 methyl 5 methoxy 4 oxy 1:1 azobenzene-5-carboxylicacid-3-su'lphonic acid,

4 amino 2 methyl 4' oxy 1:1 iazobenzene 5 canboxylic .acid-3'-sulphonicacid,

4 amino 3 methyl 4' oxy 1:1 az-obenzene 5- carboxylic acid-3'-sulphonicacid,

4 amino 2 bromo 4' oxy 1:1 azobenzene 5- carboxylic ac'id6-sulphonicacid,

4 amino 2:6 dibromo 4 oxy 1:1 azobenzene- 5'-carboxylic acid,

4 amino 2 methyl 5 methoxy 2 oxy 1: 1 azobenzene-3-carboxylic acid,

4 amino 3 methyl 2' oxy 1::1 azobenzene 3- carboxylic acid-5 -sulphonicacid,

4 amino 2 methyl 5 methoxy 5 nitro 2 oxy- 'l :=1-azobenzene-3-carboxylicacid,

4 amino 2 methyl 3' oxy 1:1 azo'benzene 4'- carboxylic acid,

4 amino 3 methyl 3' oxy 1:1' azobenzene 4- carboxylic acid.

The process of the invention also includes reacting a mixture of atleast two different amino-azo-dyestufis of the above general formulawith a sulphonic acid chloride of phthalocyanine tet'ras-ulphonic acidas defined above.

The reaction of the sulphonic acid chlorides of the phthalocyaninesulphonic acids with the aminoazodyestuffs is carried out in an aqueousmedium and in the presence of at least one substance capable of bindingmineral acid such, for example, as an alkali metal hydroxide, analkaline earth metal hydroxide, an alkali metal carbonate, an alkalineearth metal carbonate, an alkali metal bicarbonate, magnesium oxide,sodium acetate, ammonia, ammonium carbonate, dimethyl-formamide,triethanolamine, pyridine or the like.

The reaction temperature is of minor importance and may vary within Widelimits, but it is of advantage to work at a low temperature,advantageously within the range of 0-30 C.

Depending on the reaction temperature and the substance capable ofbinding mineral acid which are used, hydrolysis of the sulphonic acidchloride groups during the reaction, which can never be wholly avoided,can be checked to a greater or less degree. It is not absolutelynecessary that all the sulphonic acid chloride groups should react withthe amino-azo-dyestufi. It is often of advantage, with respect to itssolubility that the dyestufi' should contain one or more free sulphonicacid groups.

The various sulphochlorides used in the process may be reacted with atleast one, and advantageously several, molecules of amino-azo-dyestuffs.Thus, for example, 1 molecular proportion of phthalocyaninetetrasulphonic acid chloride may be reacted with 1, 2, 3 or 4 molecularproportions of an amino-azo-dyestufi.

In many cases it is uncertain whether the sulphonic acid chloride groupsare completely or only partially converted into the sulphonic acidamides of the invention.

Depending on the choice of the phthalocyanine sulphonic acid chlorideused and on the number (1 to 4) of molecular proportions ofamino-azo-dyestuff used for the reaction, there are obtained dyestuffshaving different tinctorial properties. The greater the number ofsulphonic acid groups in the dyestufi molecule the more pronounced isthe substantive character of the dyestutf, and the greater the number ofsalicylic acid groups in the dyestutf molecule the more pronounced isthe mordant character of the dyestuff, which causes a progressivelyincreasing improvement in the properties of wet fastness, The dyestufisyield green to olive tints which are in part distinguished by remarkableproperties of wet fastness and excellent fastness to light.

The alkali metal salts of the azo-phthalocyaninc dyestuffs of theinvention are easily soluble in water, and are suitable for dyeing orprinting vegetable, animal or wholly synthetic fibres, and also fordyeing oxidic protective coatings on aluminium.

Furthermore, if they contain a sufiicient number of mordanting elements,the new dyestufis can be fixed, according to known methods, on textilefibres by an aftertreatment with metal-yielding substances, if desiredtogether with high molecular basic substances. Thus, in particular,green to olive dyeings having good fastness properties to washing and tolight are obtained by after treating prints on fibres of cellulose orregenerated cellulose with copper-yielding substances together with highmolecular basic condensation products.

The following examples illustrate the invention, the parts being byweight:

Example 1 96.9 parts mol) of freshly prepared copperphthalocyaninetetrasulphochloride (crude product) obtained by reactingcopper-phthalocyanine with chlorosulphonic acid, are discharged on toice and the reaction product which separates out is mixed in the form ofa moist paste with 300 parts of broken ice. A solution of 27.9 partsmol) of the sodium salt of 3-aminc-4'- oxy-l:1-azobenzene-5'-carboxylicacid (obtained by the a reaction of diazotized 3-nitraniline withsalicylic acid followed by reduction of the nitro group with sodiumsulphide) in 300 parts of water, to which has been added 30 parts ofcalcium carbonate, is rapidly added while stirring, and the whole isstirred well at l52() C. for 24 hours, then acidified with dilutehydrochloric acid until the reaction is acid to Congo, and theprecipitated dyestutt acid is separated otf, if desired, subjected topurification, and isolated in the form of its sodium salt.

The dyestufi so obtained is a dark grey powder which dissolves in waterwith a greenish blue coloration and in concentrated sulphuric acid witha yellow-green coloration and dyes pre-chromed cotton powerful greentints having good properties of wet fastness and very good fastness tolight. In chrome printing on cotton there are produced green tintshaving good properties of fastness.

Instead of the sodium salt, the potassium, lithium or ammonium salt canbe made with the same success.

By using, instead of mol of 3-arnino-4'-oxyl:l'- azobenzene-5-carboxylicacid, mol, 0 mol or mol of 3-amino-4'-oxy-l:1'-azobenzene-5-carboxylicacid, there are obtained dyestuffs which exhibit different properties ofwet fastness, for example, in chrome printing on cotton. Thus, as thenumber of salicylic acid groups in the dyestutf molecule increases theproperties of wet fastness generally show a distinct improvement.Moreover, as the number of azo linkages in the dyestutl moleculeincreases the tint of the dyeing generally changes from blue-greentowards yellow-green or towards olive.

Of special interest is the dyestufi? obtained by reacting A mol of3-amino-4-oxy-l:l'-azobenzene-5'-carboxylic acid with A0 mol ofcopper-phthalocyanine tetrasulphochloride.

The sodium salt of this dyestutf of the formula 3:3:3"z3-tetrasulphonicacid, is a dark green dyestuft which dissolves in water with agreen-blue coloration and in concentrated sulphuric acid with a yellowcoloration. In chrome printing on cotton it yields green tints havingvery good properties of wet fastness and an excellent fastness to light.

Example 2 .96.9 parts r'riol) p'hochloride, obtained as described inExample 1, are discharged on to ice, and the reaction product whichseparates is mixed in the form o't" a moist paste with 300 .parts .ofbroken ice, and a solution, heated to 6070 (3.,

of 83.7 parts.. moi) of the sodium salt of 4-amino-4-oxy-l:1-azob'enzene 5-carboxylic acid (obtained by the reaction ofdiazotized 4-nitranil-ine with salicylic acid followed by reduction ofthe nitro group with sodium sulphide) in 2900 parts of water and 30parts of sodium .of copper phthalocyan-ine tetrasuh The dyestuff issuitable for dyeing cotton and viscose, I

and also for dyeing prechromed cotton and chromed wool.

Green tints having good properties of wet fastness and very goodfastness to light are obtained. In chrome printing on cotton green tintshaving very good properties of fastness are obtained.

Instead of 30 parts of sodium carbonate, there may be used with equalsuccess 50 parts of potassium carbonate or parts of ammonium carbonate.

Eicample 3 48.5 parts mol) of copper-phthalocyanine tetra-.sulphochloride obtained as described in-Ex ample 1, are

discharged on to ice and the reaction product which .sep-

arates -is mixed in the form of a moist paste with 200 parts of brokenice, and a so1ution,.heated to 30 C., of 38.1 parts mol) of the sodiumsalt of 3-aminoa4-oxy- 1:1'-azobenzene-5'-carboxylic acid-G-sulphonicacid (obtained by the reaction of 3-nitraniline-6-sulphonic acid withsalicylicacid followed by reduction of the amino group with sodiumsulphide) in 300 parts of water and 10 parts of sodium hydroxide(100percent) israpidly added while stirring. The mixture is stirred fora further 24 hours at room temperature, the dyestufi acid is isolated byacidification with dilute hydrochloric acid, and the dyestuif acid isconverted into its sodium salt, which is purified by repeated saltingout.

The dyestuff so obtained is a dark grey powder which dissolves in waterwith a turquoise blue coloration and in concentrated sulphuric acid witha yellow green coloration.

The new dyestuti is suitable for dyeing cottonand viscose, and also fordyeing wool. It yields green tints possessing moderate properties of wetfastness and medium fastness to light. or Wool, there are obtainedsubstantially stronger green tints which are distinguished by goodproperties of wet fastness and very good fastness to light. In chromeprinting on cotton there are obtained green tints having good propertiesof fastness.

Instead of 10 par-ts of sodium hydroxide 100 percent) there may be used15 parts of potassium hydroxide 100 percent).

Example 4 48.5 parts moi) of copper-phthalocyanine tetrasulphochlorideare prepared in a manner analogous to that described in Example l, andthe paste so obtained is introduced rapidly into a solution of 76.2parts (3 mol) of the sodium salt of 4-amino-4-oxy-l:1-azobenzene-S'-carboxylic acid-6-sulphonic acid (obtained by the reaction of4-nitraniline-6-sulphonic acid with salicylic acid followed by reductionof the nitro group with sodium sulphide) in 400 parts of water and 25parts of pyridine, and

By after-chroming dyeings on cotton Example the whole is stirred for 24hours at 0-10" C. The dyestufi acid is separated ofiin the usual manner,freed from .adherent impurities, and isolated in the form of its sodiumsalt.

The dycstufi so obtained is a dark grey powder which dure is the same asthat given in Examples 1 to 4, and 1 molecular proportion ofcopper-phthalocyanine tetrasulphochloride, obtained as described inExample 1, is reacted with the amino-azo-dyestutfs given in the thirdcolumn, the dyestufi being used in the proportion given in the secondcolumn.

Water-soluble salt of the aminoazo-dyestuti' Tint in chrome Printing 011cotton Mols bluish green.

. .do green.

3-amino-4-oxy -1:1-azo-beu- Do.

zene 5' carboxylic acid 4 sulnhonic acid.

do do 3 amino 3 methyl 4 oxy 1:

l azobenzene 5 carboxyli'c acliid 4 sulphonic acid. I o 3 amino 4 methyl4' oxy 1: 1 nzohenzene 5 carboxylic aci H on Do. yellowish green. bluishgreen.

green. grass QIGHII.

lob:

2 3 amino 6 -mctayl 4 oxy 1: bluish green.

1 nzobenzene 5 carboxylic acid.

14 l 3-amino 6 -'methoxy-4 0w 1: green.

2 do. Do.

grass green green.

0x azobenzone 5' carboxylic acid 5 sulphonic acid.

2 yellowish green. 3 do yellow green. 1 4-amino-2-n1ethyl 4-oxy-l: Do.

1 azobenzcne 5 carboxylic acid. 3 ..d0 grass green. 1 4 amino 2 methoxy4 oxy 1: green.

1 azobenzcnc 5 carboxylic acid. 25 3 do olive green. 26 1 4 amino 2:5diethoxy 4 oxy green.

1:1 azobenzene 5' carboxylic acid. 27 3 .do D0. 28 l 4 amino 2 chloro 4oxy 1: D0.

1 azobenzene 5 carboxylic acid. 29 3 ..do yellowish green. 30 1 4 amino2 nitro 4' oxy 1:1 bluish olive.

azobenzene 5 carboxylic acid. 31 3 d olive. 32 l 4 ami oxy 1:1azobenturquoise blue.

zenc :5f dicarboxylic acid. 33 3 do blue green. 34 14-amino-2-methyl-4-oxy-1: green.

1 azobenzene 5 carboxylic acid 3 sulphonic acid. 35 3 d0 yellow green.36.. 1 4 amino 3 -methyl- 4 oxy 1: jade green.

1' azobenzene 5' carboxylic acid 3 sulphonic acid. 37 3 .do yellowishgreen. 38 1 4 ammo 2 methyl 5 methoxy bluish green.

, 4 oxy 1:1 azobenzene 5 carboxylic acid 3 sulphonic acid. 39 3 do olivegreen. 40 2 4 amino 2 bromo 4 oxy l: green.

azobenzene 5 carboxylic acid 6 sulphonic acid. 41 1 4 amino 2 methyl 5methosy bluish green.

2' oxy 1:1 azobenzeno 3 carboxylic acid. 42 3 d0 olive.

Example 43 48.5 parts 5 mol) of copper-phthalocyanine-4:4:4:4-tetrasulphochloride, obtained by the action of chlorosulphonicacid on copper phthalocyanine 4:4:4":4' tetrasulphonic acid, are wellmixed with 250 parts of broken ice, and a solution of 55.8 parts ,5 mol)of the sodium salt of 3-amino-4-oxy-l:1'-azobenzene-5-carboxylic acid in300 parts of water and 35 parts of sodium acetate is rapidly added whilestirring. The whole is maintained at 20-25 C. for about 60 hours, whilestirring. The reaction mixture is rendered weakly acid with dilutehydrochloric acid, and the precipitated dyestuff acid is separated off,dis solved hot in water and sodium carbonate, and isolated in the formof its sodium salt by salting out with sodium chloride. 7

The resulting dyestutf is a dark grey powder which dissolves in waterwith a green coloration and in sulphuric acid with a dirty yellowcoloration.

The new dyestufi is suitable for dyeing cotton, viscose, wool andnatural silk. By after-treatment with a metal salt the properties of wetfastness are in part substantially improved. In chrome printing oncotton there is obtained a bright green tint having very good propertiesof wet fastness and an excellent fastness to light.

The same dyestufl. having the same tinctorial properties is obtained byworking, for example, at 0-10 C. or 50-60 C. or 80-90 C., instead of at20-25 C. as in this example.

Example 44 97 parts A mol) of copper-phthalocyanine-4:4':4":4'-tetrasulphochloride, obtained by the action ofchlorosulphonic acid on copper phthalocyanine 4:4:4":4 tetrasulphonicacid, are stirred with 400 parts of broken ice and 150 parts of water toa homogeneous paste, the latter is rendered neutral with calciumcarbonate, and then a solution of 83.7 parts 5 mol) of the sodium saltof 3-amino-4-oxyl:l'-azobenzene-5-carboxylic acid in 1000 parts ofwater, to which 40 parts of calcium carbonate have been added, is addedrapidly while stirring. The Whole is stirred for 10 hours at 5-l5 C. andthen for a further 24 hours at room temperature. When the reaction hasfinished the precipitated dyestuff is filtered oti with suction andpasted with 400 parts of water, then acidified with 400 parts ofconcentrated sulphuric acid, isolated, taken up in 300 parts of water,brought into solution with sodium carbonate, filtered, and the filtrateis salted out with 300 parts of sodium chloride. The dyestuff which isseparated in the form of its sodium salt is dried and extracted withalcohol for further purification.

The resulting dye-stuff of the formula OOONa SO3NH which is a derivativeof copper-phthalocyanine-4:4:4": 4"'-tetrasulponic acid, is a blue-blackpowder which dissolves in water with a green blue coloration and inconcentrated sulphuric acid with a yellow olive coloration. It issuitable more especially for chrome printing on cotton. There areobtained full green tints having excellent properties of fastness and aremarkable fastness to light.

By using only 7 mol, instead of mol, of 3-amino-4-oxy-1:1-azobenzene-5-carboxylic acid, there is obtained a dyestuff ofthe formula COONa 48.5 parts (l mol) of copper phthalocyanine-4:4:4":4-tetrasulphochloride, obtained as described in Example 43, are mixedwith 250 parts of broken ice and a solution of 27.9 parts A mol) of thesodium salt of 4-amino-4'- oxy-l:1'-azobenzene-5'-carboxylic acid in 600parts of water and 25 parts of magnesium carbonate is rapidly addedwhile stirring, and the mixture is stirred for 60 hours at 2030 C. Thedyestuif is isolated and worked up in the manner described in Example43.

The resulting dyestufi is a dark grey powder which dissolves in waterwith a green coloration and in concentrated sulphuric acid with agreenish yellow coloration.

The dyestuff dyes chromed cotton powerful green tints and dyesafter-chromed wool green tints which are very fast to light.

In chrome printing on cotton a strong green tint having good propertiesof fastness is obtained. Instead of 25 parts of magnesium carbonate,there may be used 12 parts of magnesium oxide, 30 parts of calciumcarbonate or 60 parts of barium carbonate.

to form a homogeneous paste. A solution of 57.1 parts mol) of the sodiumsalt of 3-amino-4'oxy-1:l-azobenzene-5-carboxylic acid-6-sulphonic acidin 400 parts of water and 25 parts of ammonia solution of 20 percentstrength is then added, and the whole is stirred for 60 hours at 0-5 C.The reaction product is salted out directly with sodium chloride, theprecipitated dyestuti is separated ofi, and is isolated in the form ofits sodium salt by reprecipitation twice.

The dyestuif so obtained is a dark green powder which dissolves in waterwith a green coloration and in concentrated sulphuric acid with agreenish-yellow coloration, and dyes chromed cotton bright bluish greentints having good properties of wet fastness and a very good fastness tolight.

In chrome printing on cotton strong green tints having good propertiesof wet fastness and a very good fastness to light are obtained.

The dyestufi produces a clear green tint on anodically oxidizedaluminum.

Instead of 25 parts of ammonia solution of 25 percent strength, theremay be used with equal success 10 parts of sodium hydroxide percent) or15 parts of potassium hydroxide (100 percent).

Example 47 48.5 parts & mol) of copper-phthalocyanine'4:4':4":4'-tetrasulphochloride are mixed well with 250 parts of ice, theresulting paste is given a pH value of 6.9 by means of an ice-colddilute solution of caustic soda, and a solution of 57.1 parts 5% mol) ofthe sodium salt of 4 amino 4' oxy 1:1 azobenzene 5' carboxylicacid-6-sulphonic acid in 400 parts of water and 20 parts of sodiumbicarbonate is rapidly added. The whole is heated while stirring well to40 C., this temperature is maintained for a few hours, and the mixtureis stirred at room temperature for a further 50-60 hours. The dyestufiis salted out by means of sodium chloride from a solution which isalkaline to litmus, and the dyestutt is purified.

The resulting dyestutf is a blue-grey powder which dissolves in waterwith a green coloration and in concentrated sulphuric acid with ayellow-brown colelfation, and in chrome printing on cotton producesyellowish green tints having good properties of fastness.

Instead of 20 parts of sodium bicarbonate, there may beused l5 parts ofsodium carbonate or 25 parts of potassium carbonate.

In the examples given in the following table the procedure is similar tothat described in Examples 43-47, and 1 mol ofcopper-phthalocyanine-4:4:4":4"'-tetrasulphochloride, obtained asdescribed in Example 43, is reacted with the amino-azo-dyestufis givenin column 3, the quantity of the dyestuif being given in column 2.

Example Mols Watersoluble salt of the amino- Tint in chromeazo-dyestuflf printing on cotton 48 1 3-amino4-methyl-4-oxy-1:1-azobluish green. benzene-5-carboxylic acid. 49 2 dgreen.

3 yellowish green. 4 yellow green. 1 methyl-4-o azo grass green.

benzene-5-carboxylic acid. 53. s 2 yellowish mesh. 54 3 yellow green. 552 3-aznino-4-oxy-l:1 azobenzene- Do.

5-carboxylic acidl-sulphonic acid. 56 i 2 4-amino-4-oxy-1:1-azobenzene-Do.

5- %arboxylic acid-fi-sulphonic 8.01 57 3 tamino-2-methoxy-4'-oxy1:1-olive green.

azobenzene-5-earboxylic acid. '58 1 4-amino2-chloro-4-oxy-1: 1- bluishgreen.

azobenzene-5-carboxylic acid. 59 M 1 4-amino-2-rnethyI-5-rnethoxy-5-blue green.

nitro-2-oxy-1:1-azobenzene-3- carboxylic acid. 60 14-amino-2-methyl-3'-oxy-1: 1- Do.

azobenzene-4'-carboxylic acid. 61 i 2 4-amino-2:6-dibrom-4-oxy-1:1- Do,

azobenzene-5-carboxylic acid. 62 3 4-amino-2-nitro-'4-oxy-1:1-azoolivegreen.

' benzene-5-carboxylic acid. (i3 3 4-amino-2-brorno-4-oxy-1:1'-azogreen.

benzene 5 carboxylic .acid 6 sulphonic acid. 64 44amino-2:4-dloxy-1:1-azoolive green.

, benzene-5-carb0xylic acid.

Example 65 An ice-cold paste of 45.7 parts mol) of copperphthalocyanine'monosulphochloride trisulphonic acid (obtained by partial hydrolysisofthe copper phthalocyamine-4:4:4":4-tetrasulphochloride' described inExample 43) is mixed at -5 C. with a solution of 14 parts mol) of thesodium salt of 4-amino-4-oxy-1:1'-azobenzene-'-carboxylic acid in 400parts of water and I Example 66 64 parts mol) of brominatedcopper-phthalocyanine-4z414":4'"-tetrasulphochloride, obtained by theaction of chlorosulphonic acid and thionyl chloride on brominated copperphthalocyanine-4:4':4":4"'-tetrasulphonic acid (containing 9.4 percentof bromine by analysis), are discharged on to ice, and the reactionproduct is filtered oil with suction .and mixed with 250 parts of brokenice. There is .then added rapidly, while stirring, a solution of '42parts (9 mol) of the sodium salt of 3-amino-4 oxy-1:l'eazobenzene-SGcarhoxylic .acidin 5300 partsof water to which have beenadded .20 parts 0f ;cal-

cium carbonate. The whole is :Stllllfid at room temperature for 50 hours.and the-dyestuff-is isolated-as-itssod'ium salt.

The dyestuif .so obtained is .a :dark ,green powder dissolves in waterwith a bluish green coloration audio concentrated sulphuric acid with anolive coloration, and in'ehrome printing on cotton yields strong greentints having very good properties of fastness.

Example 67 A moist paste of copper-phthalocyanine tetrasulphochloride,which has been obtained by reacting chlorosulphonic acid with'45 parts1420 mol) of copper-phthalocyanine tetrasulphonic acid (obtained by the.sulphonation of copper-phthalocyanine with oleurn), discharging themixture on to broken ice and separating the reaction product, is mixedwith parts of ice and 100 parts of 'water. There is added rapidly, whilestirring, a solution Example 68 24.2 parts mol) of copper-phthalocyauinetetrasulphochloride, obtained as described in Example 1, are dischargedon to ice and the sulphochloride which separates out is stirred in theform of .a moist paste with parts of shroken ice. There is then addedrapidly while stirring a solution of 22.2 parts i mol) of the sodium.salt of 4-amino-2:4'-diox-y-l:lazobenzene-5'- .canboxylic acid (obtainedby coupling d-iazotized paraamino-acetanilide with 2:4-dioxyben-zoicacid followed by hydrolysis).,in 400 parts .of water and 15 parts ofmagnesium carbonate, and the Whole is stirred for 24 hours at roomtemperature. The dyestuif is isolated by acidification with dilutehydrochloric acid, is purified by reprecipitation and washing, andisolated as its sodium salt.

The dyestufi" so obtained is a dark grey powder :which dissolves inwater with .a dark green coloration and in concentrated sulphuric acidwith a yellow :brown coloration. I

The new dyestuif dyes cotton directly strong greenish grey tints anddyes chromed cotton strong grey-green tints. It dyes nylon olive browntints and anodically oxidised aluminum green tints. In chrome printingon cotton there are produced olive tints having remarkable properties offastness.

Example .69

96.0 parts A0 mol) of copper-phthalocyanine tetrasulphochloride,obtained as described ,in Example 1, are mixed in the form of a moist,paste with 350 parts of broken 'ice, and there is rapidly added asolution of 27.9 parts -rno'l9 of .the sodium salt of 4-a1nino-4-oxy-1:l-azobenZene-5-carboxylic acid, 29.3 parts mol) of the sodium salt of3-'a.mino-,2-methyl-4-oxy-l:l-azobenzene-5'-carb oxylic acid (obtainedby coupling diazotized B-nitraniline with 4-methyl-2-oxybenzoic acidfollowed :by reduction with sodium sulphide) in 2000 parts of water and30 parts of sodium carbonate, and the whole is stirred for 30 hours at 0C. The isolation and working up of the azo-phthalocyanine ,dyestufi arecarried out as "described in Example 2.

The dyestuif so obtained'is a greenish dark grey powder whichdissolves-in water with a blue green coloration and inconcentrated's'ulphuric acid with a brown yellow coloration, and inchrome printing on cotton yields bright green tints having very goodproperties of fastness.

Example 70 29 par-ts (di mol) .of nickel-phthalocyaninetetrasulphochloride, obtained by :the action of chlorosulphonic acid. onmiekelsphthalocyanine, are discharged on to ice 11 and the separatedreaction product is mixed in the form of a moist paste with 150 parts ofbroken ice, and a solution of 25.1 parts (W mol) of the sodium salt of3- amino-4'-oxy-l:1'-azobenzene-5-carboxylic acid in 300 parts of waterand 15 parts of calcium carbonate is added. The whole is stirred for 24hours at -5 C., the reaction mixture is rendered weakly alkaline withsodium carbonate while heating the mixture to 50 C., the mixture isfiltered to remove calcium carbonate, and the dye stuff is salted outwith the sodium chloride. The resulting dyestufi of the formula SOsNuwhich is a derivative of nickel-phtha1ocyanine-3:3:3":

3"'-tetrasulphonic acid, is a dark grey powder which dissolves in waterwith a green coloration and in concentrated sulphuric acid with agreenish yellow coloration.

The new dyestutl is suitable for dyeing chromed cotton, whereby stronggreen tints of good fastness' to light are obtained. In chrome printingon cotton bright green Tint in Example Mols Water-soluble salt of theanliuo-azochrome (lyestufi printing on cotton 1S-amino-oxy-lzl-azobenzcue-5- blue green.

carboxyllc acid-4-snlphonic acid. 3 do yellow green. 13-amino-c-metboxy-4-oxy-l:1-azogreen.

benzene-5-carboxylic acid. 3 do olive green. 1 -i-a min 0-2-0 h 1 o 1'0-4-0xy:1-1-uz0- blue green.

benzene-5'-carboxylie acid. 76 3 do green.

Example 77 96.4 parts mol) of nickel phthalocyamne-4:4:4":4"-tetrasulphochloride, obtained by the action of chlorosulphonicacid on nickel-phthalocyanine-4:4:4":- 4- tetrasulphonic acid, are mixedwell with 350 parts of broken ice, and there is added rapidly whilestirring a solution of 83.7 parts mol) of the sodium salt of 3-amino-4-oxy-1:l-azobenzene-5-carboxylic acid in 500 parts of water, towhich is added parts of calcium carbonate, and the mixture is stirredfor about hours at 25 C. The reaction mixture is rendered weakly acidwith dilute hydrochloric acid, the precipitated dyestuif acid isseparated ofi, and dissolved in water and sodium carbonate, and thedyestuff is salted out.

The dyestuff so obtained is a blue-black powder which dissolves in waterwith a blue green coloration and in concentrated sulphuric acid with ayellow olive coloranon.

The new dyestulf yields in chrome printing on cotton full green tintshaving excellent properties of fastness.

V Example 78 48.3 parts /z mol) of freshly prepared cobaltphthalocyaninetetrasulphochloride, obtained by the action of cblorosulphonic acid oncobalt-phthalocyanine, are discharged on to ice, and the reactionproduct is separated and mixed in the form of a moist paste with 250parts of broken ice. There is then added rapidly to a solution of 41.7parts mol) of the sodium salt of 3-amino-4'-oxy-1:1-azobenzene-5'-carboxylic acid in 400 parts of water and 20parts of calcium carbonate, and the mixture is stirred for 3 hours at30-40 C. and then at room temperature for a further 24 hours. Thedyestuif is isolated as described in Example 69.

The resulting dyestufi is a blue-grey powder which dissolves in waterwith a greenish blue coloration and in concentrated sulphuric acid witha green yellow coloration.

In chrome printing on cotton there are obtained strong green tintshaving very good properties of wet fastness and an excellent fastness tolight. The dyestutf yields an anodically oxidized aluminum intense greentints.

Instead of calcium carbonate, there may be used other alkalis.

Example 79 48.3 parts & mol) of cobalt-phthalocyaninetctrasulphochloride, obtained as described in Example 78, are mixed with250 parts of broken ice, and there is added rapidly a solution of 32.4parts 4 mol) of the sodium salt of 4amino-2nitro-4'-oxy 1:1azobenzene-5'carboxylic acid (obtained by coupling diazotized4-acetylamino-Z-nitraniline with salicylic acid followed by hydrolysis)in 1000 parts of water and 20 parts of calcium carbonate. The whole isstirred for 15 hours at room temperature and the dyestuit is isolated inthe usual manner.

The dyestuff so obtained is a dark grey powder which dissolves in waterwith an olive green coloration and in concentrated sulphuric acid with agrey-brown coloration, and yields in chrome printing on cottoninteresting green tints having good properties of fastness.

By using in this example, instead of 4-amino-2-nitro-4-oxy-1:1-azobenzene-5-carboxylic acid, a corresponding quantity of4-amino-2-chloro-4-oxy-l:1'-azobenzcne- 5'-carboxylic acid or 3-amino-4oxy-l:l'-azobenzene-5- carboxylic acid 6-sulphonic acid, there areobtained dyestuffs which yield similar tints and possess good propertiesof fastness.

Example 80 96.5 parts mol) of cobalt phthalocyanine- 4:4'z4":4"-tetrasulphochloride, obtained by the action of chlorosulphonic acidon cobalt-phthalocyaninel:4':4": 4"'-tetrasulphonic acid, are introducedrapidly in the form of a moist paste at 10 C. into a solution of 29.3parts A mol) of the sodium salt of3-amino-2-methyl-4'-oxyl:1-azobenzene-5-carboxylic acid in 800 parts ofwater and 45 parts of potassium hydroxide percent). The whole is stirredfor 50 hours at 10 C., and the dycstuti" is isolated in the usualmanner.

The dyestufi is a dark grey powder which dissolves in water with a bluegreen coloration and in concentrated sulphuric acid with a greenishyellow coloration.

In chrome printing on cotton it yields bright green tints having goodproperties of fastness.

Example 81 48.1 parts (3& mol) of iron-phthalocyaninetetrasulphochloride, obtained by the action of chlorosulphonic acid oniron-phthalocyanine, are mixed well with 250 parts of broken ice, andthere is added while stirring a solution of 57.1 parts mol) of thesodium salt of 3-arnino-4- oxy-l l-azobenzene-5 -carboxylicacid-6-sulphonic acid in 400 parts of water and 15 parts of potassiumhydroxide (100 percent). The whole is stirred at room temperature for 24hours and the dyestuff is isolated in the form of its potassium salt.

azobenZeneT-carboxylic acid-d-sulphonic acid, W mol of3-amino-4'-oxy-l:1'-azobenzene 5' carboxylic acid there is obtained adyestuflf which dyes cotton in chrome printing olive green tints.

Example 82 24.1 parts 4 mol) of iron-phthalocyanine-tetrasulphochloride,obtained as described in Example 81, are mixed with 150 parts of brokenice, and the whole is introduced rapidly into a solution'of 30.9 parts,4 mol) of the sodium salt of 4-amino-3-methoxy4-oxy-1:l'-azobenzene-5-carboxylic acid in 800 parts of water, to which15 parts of magnesium carbonate are added. The whole is stirred for 40hours at 5-10 C. and the dyestuff is isolated in the usual manner. Thedyestufi is a dark grey powder which dissolves in Water with an olivegreen coloration and in concentrated sulphuric acid with a violet browncoloration.

In chrome printing on cotton it yields olive brown tints.

By using 4 mol of 4-amino-2:4'-dioxybenzene-l:1-azobenzene-5'-carboxylic acid, instead of 4 amino 3-methoxy-4'-oxy-1:1'-azobenzene-S-carboxylic acid, there is obtained adyestufi which dyes cotton in chrome printing olive green tints.

Example 83 96.2 parts A filol) of iron phthalocyanine-4:4': 4";4'"tetrasulphochloride, obtained by the action of chlorosulpho'nic acid oniron-phthalocyanine-4 :4 4" :4"'- tetrasulphonic acid, are introduced inthe form of a moist paste into a solution of 51.4 parts 7 mol) of thesodium Example 84 47.9 parts mol) of chromium-phthalocyaninetetrasulphochloride, obtained by the action of chlorosulphonic acid onchromium phthalocyanine, are discharged on to ice, and the precipitatedreaction product is mixed in the form of a moist paste with 200 parts ofice, and there is rapidly added a solution of 41.8 parts mol) of thesodium salt of 3-amino-4'-'oxy-1:l-azobenzene-5'-carboxylic acid in 400parts of water and 10 parts of sodium hydroxide (100 percent). is thenstirred at 10-20 C. for 24 hours.

The dyestufi is isolated in the form of its sodium salt in the usualmanner.

The dyestutl so obtained is a gray green powder which dissolves in waterwith a green coloration and in concentrated sulphuric acid with a yellowcoloration, and dyes cotton in chrome printing yellow-green tints havingvery good properties of wet fas'tness.

Example 85 95.8 parts mol) of chromium-phthalocyaninetetrasulphochloride, obtained as described in Example 84, are mixed inthe form of a moist paste with 200 parts of ice and 200 parts of water,and there is rapidly added a solution of 73.6 parts mol) of the sodiumsalt of 4 amino 2 methyl 5 methoxy 2' oxy 5 nitro- The whole 14l:1'-azo-benzene-3'-carboxylic acid (obtained by coupling diaz otized5-nitro-3-amino-2-oxybenzoic acid in acetic acid with S-methyl-Z-methoxyaniline) in 1200 parts of Water and 30 parts of sodium carbonate. Thewhole is stirred for 24 hours at room temperature, and the dyestuff isisolated in the usual manner.

The dyestulf so obtained is a dark grey powder which dissolves in waterwith a green coloration and in concentrated sulphuric acid with ared-browncoloration, and dyes cotton in chrome printing olive greentints.

Example 86 47.9 parts mol) of chromium phthalocyanine-4:424":4"'-tetrasulphochloride, obtained by the action ofchlorosulphonic acid on chromium phthalocyanine- 4:4:4:4"-tetrasulphonicacid, are discharged on to ice, and the precipitated reaction product israpidly added in the form of a moist paste to a solution of 42 partsmol) of the sodium salt of 3-amino-4'-oxy-1:1'-azobenzene-5'-carboxylicacid in 300 parts of water, to which have been added 20 parts of calciumcarbonate. The whole is first maintained at 10 C. for 10 hours and thenstirred for 40 hours at 20-25 C. The dyestufii is isolated in the usualmanner in the form of its sodium salt.

The dyestutf so obtained is a dark green powder which dissolves in waterwith a green coloration and in sulphuric acid with a yellow-browncoloration.

The new dyestufi yields in chrome printing on cotton olive green tintshaving very good properties of fastness.

Example 87 93.3 parts mol) of aluminium-phthalocyaninetetrasulphochloride, obtained by the action of chlorosulphonic acid onaluminium-phthalocyanine, are discharged on to ice, and the isolatedreaction product is mixed in the form of a moist paste with 400 parts ofbroken ice, and there is rapidly added a solution of 83.7 parts A mol)of the sodium salt of 3-amino-4-oxy-l:1-azoben- Zene-5-carboxylic acidin 500 parts of water and 20 parts of sodium hydroxide percent). Thewhole is stirred for 24 hours at 20 C. The resulting solution mixed withsodium chloride, and the precipitated dyestufi is isolated and purifiedby being salted out twice.

The dyestutf so obtained is a greenish dark grey powder which dissolvesin water with a green coloration and in concentrated sulphuric acid,with a green-yellow coloration, and dyes cotton in chrome printingbright green tints having very good properties of wet fastness.

The dyestufl yields on anodically oxidised aluminium a beautiful bluishgreen tint.

Instead of 3-amino-4-oxy-1:1-azobenzene-5-caroxylic acid, there may beused with equal success 3-amino-4- oxy-l 1'-azobenzene-5'-carboxylicacid-o-sulphonic acid.

Example 88 28 parts mol) of aluminium-phthalocyanine-4:4z4":4"-tetrasulphochloride, obtained by the action of chlorosulphonicacid on aluminium-phthalocyanine- 4:4:4:4"-tetrasulphonic acid, arestirred with parts of broken ice and 200 parts of Water. To theresulting paste is added a solution of 23.1 parts mol) of the sodiumsalt of 4-arnino-4'- oxy-l:1'-azobenzene-5'-carboxylic acid in 700 partsof water and 20 parts of potassium carbonate, and the whole is stirredfor 50 hours at room temperature. The dyestufl? is isolated in the usualmanner.

The dyestutl is a greenish dark grey powder which dissolves in waterwith a yellow green coloration and in concentrated sulphuric acid with abrown coloration, and dyes cotton in chrome printing green tints.

The expression oxy means throughout the specification hydroxyl.

What we claim is:

1. A process for .themanufacture of water-soluble mordantazo-phthalocyanine dyestuflfs comprising the step of condensing onemolecular proportion of a phthalo cyanine sulphochloride of the generalformula no NH:

nooo

in which ,r stands for a. member selected from the group consisting ofhydrogen, chlorine, bromine, a methyl, hydroxyl, nitro and sulphonicacid group, y stands for a member selected from the group consisting ofhydrogen, chlorine, bromine, an alkyl, alkoxy, nitro, sulphonic acid andcarboxylic acid group and 2 stands for a member selected from the groupconsisting of hydrogen, chlorine, bromine, an alkyl and alkoxy group.

2. A process for the manufacture of water-soluble mordantazo-phthalocyanine dyestuffs comprising the step of condensing onemolecular proportion of a phthalocyanine sulphochloride of the generalformula in which A represents a metahcontaining phthalocyanine nucleus,in which the -SO2Cl and SO3I-I groups are present in one of the 3- and4-positions, said metal being selected from the group consisting ofcopper, cobalt, nickel, iron, chromium and aluminum, It stands for aninteger from 2 to 4 inclusive, and m is a numeral from to 2 inclusive,the sum of m-l-n being equal to 4, in an aqueous medium and in thepresence of a mineral acid binding agent with 2 to 4 molecularproportions of at least one amino-azo dyestuff of the general formula HONH:

HOOC

in which it stands for a member selected from the group consisting ofhydrogen, chlorine, bromine, a methyl, hydroxyl, nitro and sulphonicacid group, y stands for a member selected from the group consisting ofhydrogen. chlorine, bromine, an alltyl, alkoxy, nitro, sulphonic acidand carboxylic acid group and z stands for a member selected from thegroup consisting of hydrogen, chlorine, bromine, an alkyl and alkoxygroup.

3. A pr. for the manufacture of water-soluble mordant archthalocyaninedyestufis comprising the step of condensing one molecular proportion ofa phthalocyaninc sclphcehloride or. the general formula --(SOsH)m inwhich A represents a metal-containing phthalocyanine nucleus, in whichthe SO2C1 and -SO3H groups are present in one of the 3- and 4-positions,said metal being selected from the group consisting of copper, cobalt,

nickel, iron, chromium and aluminum, n stands for an integer from 2 to 4inclusive, and m is a numeral from 0 to 2, the sum of m+n being equal to4, in an aqueous medium and in the presence of a mineral acid bindingagent with 2 to 4 molecular proportions of at least oneamino-azo-dyestuff of the formula 1 COOH HrN 4. A process for themanufacture of a water-soluble mordant azo-phthalocyanine dyestutlcomprising the step of condensing one molecular proportion of copperphthalocyanine-3 3 3" 3"'-tetrasulphochloride in an aqueous medium andin the presence of a mineral acid binding agent with 3 molecularproportions of 3-arnino- 4-hydrony-l l.azobenzene-5-carboxylic acid.

5. A process for the manufacture of a watersoluble mordantazo-phthalocyanine dyestuif comprising the step of condensing onemolecular proportion of copper phthalocyanine-4 4 4"4"-tetrasulphocl1loride in an aqueous medium and in the presence of amineral acid binding agent with 3 molecular proportions of 3-amino-4'-hydroxy'l 2 l -'1zobenzene-5-carboxylic acid.

6. A process for the manufacture of a water-soluble mordantazo-phthalocyanine dyestuff comprising the step of condensing onemolecular proportion of copperphthalocyanine-4:4:4":4-tetrasulphochloride in an aqueous medium and inthe presence of a mineral acid binding agent with 2 molecularproportions of 3-arnino-4'- hydroxy-l l-azobenzene'5'-carboxylic acid.

7. A process for the manufacture of a water-soluble mordantazo-phthalocyanine dyestuff comprising the step of condensing onemolecular proportion of nickel phthalocyanine-3 :3: 3"3-tetrasulphochloride in an aqueous medium and in the presence of amineral acid binding agent with 3 molecular proportions of 3-amino-4-hydroxy-l l-azobenzene-5'-carboxylic acid.

8. Water-soluble mordant azo-phthalocyanine dyestuffs corresponding tothe general formula in which A represents a metal-containingphthalocyanine nucleus, in which the SO2.NH and SO3H groups are presentin one of the 3- and 4-positions, said metal being selected from thegroup consisting of copper, cobalt, nickel, iron, chromium and aluminum,n stands for an integer from 1 to 4 inclusive, m stands for a numeralfrom O to 3 inclusive, the sum of m+ri being equal to 4, x stands for amember selected from the group consisting of hydrogen, chlorine,bromine, a methyl, hydroxyl, nitro and sulphonic acid group, y standsfor a member selected from the group consisting of hydrogen, chlorine,bromine, an alkyl, alkoxy, nitro, sulphonic acid and carboxylic acidgroup and 2 stands for a member selected from the group consisting ofrydrogcn, chlorine, bromine, an alkyl and alkoxy group, and the -SO2.NHgroup occupies one of the metaand para-positions relatively to the 2120linkage.

9. The water-soluble mordant aZo-phthalocyanine dye- E SO2.HN

COONB 17 18 in which A stands for the copper phthalocyaninein which Astands for the copper phthaloc'yariine 3:3:3":3"-tetrasulphonic acidmolecule. 4:4'z4":4"'-tetrasulphonic acid molecule.

10. The water-soluble mordant azo-phthalocyanine 12. The water-solublemordant azo-phthalocyanine dyestuif of the formula dyestuif of theformula E S02.HN N: ()H E smHN- N=N OH COONa 3 OOONa -SO:N8 10 -SO3N8 inwhich A stands for the copper phthalocyaninein which A stands for thenickel phthalocyanine- 4:424":4"'-tetrasulphonic acid molecule.3:3'23:3"'-tetrasulphonic acid molecule.

11. The Water-soluble mordant azo-phthalocyanine dyestuif of the formula15 References Cited in the file of this patent UNITED STATES PATENTS ESOmHN N=N 0H 2,187,716 Hartmann Jan. 23, 1940 2,414,374 Haddock Jan. 14,1947 CON;

1. A PROCESS FOR THE MANUFACTURE OF WATER-SOLUBLE MORDANTAZO-PHTHALOCYANINE DYESTUFFS COMPRISING THE STEP OF CONDENSING ONEMOLECULAR PROPORTION OF A PHTHALO CYANINE SULPHOCHLORIDE OF THE GENRALFORMULA